Aromatic dicarboxylic acid diallyl ester derivatives, prepolymer derived from the derivative and curable resin composition containing the derivative

ABSTRACT

A diallyl aromatic dicarboxylate derivative of the formula ##STR1## wherein Y is hydrogen atom or perfluoroalkenyl group having 6 to 14 carbon atoms, is a novel compound. The compound (1) is a starting material for a prepolymer containing a repeating unit derived from diallyl aromatic fluorine-containing dicarboxylate and represented by the formula ##STR2## wherein X is perfluoroalkenyl group having 6 to 14 carbon atoms. Further, the present invention provides a curable resin composition which comprises a prepolymer having at least one carbon-carbon double bond in the molecule and diallyl aromatic fluorine-containing dicarboxylate represented by the formula ##STR3##

This is a division, of application Ser. No. 338,835 filed Apr. 14, 1989,now U.S. Pat. No. 5,061,770, which is a division of Application Ser. No.109,413 filed Oct. 19, 1989, now U.S. Pat. No. 4,841,093.

The present invention relates to an aromatic dicarboxylic acid diallylester derivative, prepolymer derived from the derivative and curableresin composition containing the derivative.

It is known that a hexafluoropropene oligomer is reacted with4-hydroxyphthalic acid or 5-hydroxyisophthalic acid to obtain acorresponding [perfluoroalkenyloxy] (iso)phthalic acid (JapaneseUnexamined Patent Publication Nos. 140,951/1981 and 51,146/1985).Further, also is known a dialkyl ester of 4-perfluoroalkenyloxyphthalicacid (Japanese Unexamined Patent Publication No. 24,547/1986). However,these compounds have no double bond in the molecule and can notpolymerized by themselves or with other compounds having a double bond.

Diallyl aromatic dicarboxylate such as diallyl phthalate is a monomerhaving two polymerizable functional groups and is used for preparing athermosetting resin. In a molding process for obtaining a desired moldedarticle by polymerizing such a monomer, having at least twopolymerizable functional groups, into a polymer, it is usual to suspendthe polymerization reaction before completion in order to obtain apolymer having solubility in solvent or having thermoplasticity. Thepolymer is molded as in the form of a solution or a thermoplastic resin,and then polymerization is completed (cured) after molding or at thesame time as molding to a cured resin which is not soluble in solventsor isthermoplastic. In the above method, the polymer having solubilityor thermoplasticity is called a prepolymer.

A cured article of a conventional prepolymer, such as diallyl phthalate,is useful as a socket, connector and like electric parts, laminates,decorative sheets, etc., but has a defect of being poor inwater-resistance.

Further, various curable resin compositions are conventionally known andare used for inks, varnishes, coating compositions, adhesives, FRP,molded articles and the like. An epoxy acrylate resin is excellent inadhesion to various kinds of substrates but is inferior inwater-resistance. Further, an unsaturated polyester has a defect ofbeing insufficient in water-resistance.

An object of the invention is to provide a novel aromatic dicarboxylicacid diallyl ester derivative and a process for preparing the same,which derivative has a double bond and can polymerize by itself or withother compounds having a double bond.

Another object of the invention is to provide a novel prepolymer derivedfrom diallyl aromatic dicarboxylate which affords a cured product havingan excellent water-resistance.

Still another object of the invention is to remedy the above-mentioneddefects and to provide a curable resin composition which hardens byheating or irradiation of active energy rays to give a cured articlehaving an excellent water-resistance.

The present invention provides a diallyl aromatic diacarboxylatederivative of the formula ##STR4## wherein Y is hydrogen atom orperfluoroalkenyl group having 6 to 14 carbon atoms.

The above diallyl aromatic dicarboxylate derivative includes all of theisomers in which one 2-propenyloxycarbonyl group is bonded in the ortho,meta or para position with respect to the other 2-propenyloxycarbonylgroup.

Examples of perfluoroalkenyl groups Y having 6 to 14 carbon atoms of theinvention are the following groups of the formulae: ##STR5## wherein R¹,R² and R³ are each perfluoroalkyl group having 1 to 6 carbon atoms, orone of them is fluorine atom and the others are each perfluoroalkylgroup having 1 to 6 carbon atoms, R⁴ is perfluoroalkyl group having 1 to5 carbon atoms. Especially preferable are groups formed by eliminatingone fluorine atom from a dimer or trimer of hexafluoropropene, ortetramer, pentamer, hexamer or heptamer of tetrafluoroethylene. Thesegroups are shown below by the formulae. ##STR6##

In the invention, the compound (3) of the formula ##STR7## is novel andis prepared, for example, by reacting a perfluoroalkene XF with ahydroxy aromatic dicarboxylic acid derivative of the formula ##STR8##

In the above formulae, X is a perfluoroalkenyl group having 6 to 14carbon atoms.

The above compound (2) is novel and is obtained, for example, byesterifying a hydroxyphthalic acid with allyl alcohol in the presence ofa catalyst. In the reaction, allyl alcohol is used preferably in anamount of about 2 to 40 moles per mole of hydroxyphthalic acid. As acatalyst is used concentrated sulfuric acid, p-toluenesulfonic acid,boron trifluoride ethyl etherate, etc. The reaction temperature ispreferably about 50° to 200° C., the reaction time is suitablydetermined and is generally about 30 minutes to 20 hours. The reactionpressure is not particularly limited. The reaction is conductedpreferably in a solvent there. As a solvent is preferably used one whichmake an azeotrope with water and is substantially immiscible with water.Examples thereof are benzene, toluene, xylene, diallyl ether, etc. Theobtained compound (2) can be purified by known method such asconcentration, extraction, distillation, chromatography, etc. but can bereacted without purification with the perfluoroalkene XF in a nextprocess step.

Examples of perfluoroalkenes XF are the following compounds of theformula: ##STR9## wherein R¹, R² and R³ are each a perfluoroalkyl grouphaving 1 to 6 carbon atoms, or one of them is a fluorine atom and theothers are each a perfluoroalkyl group having 1 to 6 carbon atoms.Especially preferable are a dimer or trimer of hexafluoropropene, ortetramer, pentamer, hexamer or heptamer of tetrafluoeroethylene. Theseare shown below by the formulae: ##STR10##

The reaction is conducted preferably in a solvent in the presence of abase. Examples of bases are triethylamine, trimethylamine,tripropylamine or like amines, alkali metal or hydroxides thereof, etc.As a solvent is used preferably an aprotic polar solvent such asacetonitrile, dimethyl formamide, dimethyl sulfoxide, etc. Theperfluoroalkene is used preferably in an amount of about 1 to 10 molesper mole of the compound (2). The reaction temperature is suitablyselected but is usually about 0° to 40° C., preferably about 0° to 20°C. The base is used preferably in an amount of about 2 to 20 moles permole of the compound (2). The desired compound (3) can be separated andrecovered by known methods used in the separation of a mixture oforganic compounds containing solid dissolved in liquid. For example, thereaction mixture is added to a large amount of diluted hydrochloric acidand the resulting precipitates are collected and distilled at a reducedpressure to obtain the desired compound.

The compounds XF of the formula (5) include compounds represented by theformulae below. ##STR11##

From the above compounds, the following groups are producedrespectively. ##STR12##

More specifically, from the compound ##STR13## the following group isformed. ##STR14##

Further, the compound (1) can also be prepared by reacting an allylalcohol with an aromatic dicarboxylic acid of the formula ##STR15##wherein Y is hydrogen atom or perfluoroalkenyl group having 6 to 14carbon atoms. The compound (4) is a known compound. The reaction isconducted preferably in a solvent. As a solvent is preferably used onewhich makes an azeotrope with water and is substantially immiscible withwater. Examples thereof are benzene, toluene, xylene, diallyl ether,etc. Allyl alcohol is used preferably in an amount of about 2 to 10moles per mole of the compound (4). The reaction temperature is suitablyselected but is usually about 50° to 200° C., preferably about 70° to160° C. The desired compound (1) can be separated and recovered by knownmethods used in the separation of a mixture of organic compoundscontaining solid dissolved in liquid. For example, the desired compound(1) can be recovered by concentration, distillation, gas chromatography,etc.

The compound (1) can be polymerized by heating in the presence of aperoxide such as benzoyl peroxide, thereby a polymer (prepolymer) havinga double bond is prepared. The prepolymer can be cured to a resin byheating or with irradiatin of light, electron rays or the like activeenergy rays and the cured product is excellent in water-resistance.

Thus, the present invention provides a prepolymer containing a repeatingunit derived from diallyl aromatic fluorine-containing dicarboxylate andrepresented by the formula ##STR16## wherein X is perflouralkenyl grouphaving 6 to 14 carbon atoms. Examples of X are same as described above.

In the invention, the repeating unit of the formula (6) is derived fromdiallyl fluorine-containing dicarboxylate which is a monomer of theabove prepolymer and is represented by the formula ##STR17##

The compound (3) may convert, in some case, into a repeating unit of theformula ##STR18##

In the present invention, it is probable that there will be present inthe prepolymer, a small amount of the above repeating unit(s).

The present prepolymer includes a copolymer having the repeating unit ofthe formula (6) and another repeating unit.

Examples of other repeating units are those derived from cleavage ofdouble bond of various compounds such as ethylene, vinyl acetate, vinylfluoride, vinyl chloride, acrylamide, methacrylamide, styrene,α-methylstyrene, p-methylstyrene, alkyl ester of acrylic acid ormethacrylic acid, benzyl (meth)acrylate, vinyl alkyl ether, halogenatedalkyl vinyl ether, vinyl alkyl ketone, cyclohexyl (meth)acrylate, maleicanhydride, butadiene, isoprene, chloroprene, diallyl phthalate, diallylisophthalate, diallyl terephthalate, etc.

The prepolymer has a molecular weight (Mn) preferably of about 1000 to50000, more preferably about 3000 to 10000 and an iodine value (grams ofiodine which adduct to 100 g of sample) preferably of about 10 to 95,more preferably about 25 to 80. When the product has too high of amolecular weight, the gelled polymer is hard to process. With too smalla molecular weight, the cured product does not have practical strength.The prepolymer having too small an iodine value can not give a curedproduct having practical strength. A cured product having inferiorimpact-resistance is obtained from a prepolymer having too large aniodine value.

The prepolymer is prepared by polymerizing the compound (3) orcopolymerizing it with other comonomer.

Examples of useful comonomers are various compounds such as ethylene,vinyl acetate, vinyl fluoride, vinyl chloride, acrylamide,methacrylamide, stryrene, α-methylstyrene, p-methylstyrene, alkyl esterof acrylic acid or methacrylic acid, benzyl (meth)acrylate, vinyl alkylether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl(meth)acrylate, maleic anhydride and like ethylenic compounds,butadiene, isoprene, chloroprene and like conjugated diene compounds,diallyl phthalate, diallyl isophthalate, diallyl terephthalate and likenon-conjugated diene compounds, etc. The prepolymer contains therepeating unit (6) in an amount preferably of at least about one percent(weight percent, same as hereinafter), more preferably at least about10%. With less than about one percent, water-resistance is not expected.

In the polymerization, methods and conditions thereof are suitablyselected. For example, as radical polymerization are adopted bulkpolymerization, solution polymerization, suspension polymerization,emulsion polymerization, etc. As ionic polymerization are conductedcationic polymerization, etc. As an initiator in radical polymerizationis used a compound which produces free radicals. Preferred radicalinitiators are benzoyl peroxide, tert-butyl perbenzoate, acetyl benzoylperoxide, succinyl peroxide, diisopropyl peroxydicarbonate, ammoniumpersulfate and like peroxides, azobisisobutyronitrile and likeazonitriles, etc. Further, it is possible to use a chain transfer agentwhich is disclosed in Japanese Examined Patent Publication No.16,035/1960 and has the formula ##STR19## wherein Z is Cl, OH or groupconvertible to OH, R is lower alkyl (1 to 4 carbon atoms), m is 0 to 4,n is 0 to (4-m). The chain transfer agent is used in an amount ofpreferably about 10 to 25% by weight in order to adjust the molecularweight and to prevent gelation. For the same purpose the amount ofinitiator, polymerization temperature, polymerization time, etc can beadjusted. The radical initiator is used in an amount of 0.1 to 10% byweight based on the weight of monomers. However, the amount of initiatoris not limited thereabove and is suitably selected depending onpolymerization degree of the desired polymer, polymerization time,polymerization temperature, etc. The polymerization temperature isusually -80° C. to +250° C. as depending on the decompositiontemperature of the initiator. Generally, the temperature is preferablyin the range of -40° C. to +150° C. Solvents useful for solutionpolymerization are benzene, toluene, xylene and like aromatichydrocarbons, chloroform, methylene chloride, ethylene chloride and likelow-basic solvents. These solvents are used singly or in mixture. Thecationic polymerization is preferably conducted in a solvent such astoluene, benzene, etc. at -30° C. to +250° C. in the presence of borontrifluoride ethyl etherate, aluminum chloride or like initiator.

The polymer is separated from the reaction mixture by a usual method,for example, by adding the mixture to a poor solvent which does notdissolve the polymer such as methanol, diisopropyl ether, dimethylether, petroleum ether or n-hexane. The polymer is obtained asprecipitates. The precipitated polymer is purified by dissolving it in asolvent which is capable of dissolving the polymer such as acetone,methyl ethyl ketone, ethyl acetate, dioxane, tetrahydrofuran, ethylenedichloride, chloroform, carbon tetrachloride, trichloroethylene,benzene, toluene, etc. and thereafter re-precipitating the polymer byadding the solution in a poor solvent.

The present prepolymer can be cured by itself or in the form of amixture thereof with a prepolymer of diallyl phthalate, diallylisophthalate, diallyl tetraphthalate, etc. The curing is conducted byheating or light in the presence of thermal polymerization initiator,photopolymerization initiator, etc. or with irradiation of electronrays, gamma-rays or like active energy rays in the absence of theinitiator. In case of using the initiator, as a carrier for initiator isused diallyl phthalate, diallyl isophthalate, diallyl terephthalate orlike monomer. The carrier is used preferably up to about 90% by weightof the mixture.

Examples of thermal polymerization initiators are methyl ethyl ketoneperoxide, cyclohexanone peroxide and like ketone peroxides, t-butylperbenzoate, t-butyl peroxy-2-ethylhexoate and like peresters, t-butylhydroperoxide, cumene hydroperoxide and like hydroperoxides, benzoylperoxide and like diacyl peroxides. The photopolymerization initiatorsinclude 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone andlike benzoin alkyl ethers, diethoxyacetophenone and like acetophenones,benzophenone and like ketones, 2-chlorothioxanthone and likethioxanthones, etc. The initiator is used preferably in an amount ofabout 0.001 to 20% by weight, more preferably about 0.1 to 10% by weightbased on the total amount of the prepolymer and carrier.

The curing is conducted usually at a temperature from room temperatureto 250° C., preferably from room temperature to 180° C., despite thatany of heat, light or active energy rays is used.

The compound (3) which is diallyl aromatic fluorine-containingdicarboxylate is mixed with a prepolymer having at least onecarbon-carbon double bond in the molecule to form a curable resincomposition.

The followings are examples of useful prepolymers having at least onedouble bond in the molecule, although not limited thereto.

(i) Polyester obtained by using an unsaturated polybasic carboxylic acidor polyester using an unsaturated polyol

These polyesters are prepared by the condensation of a polybasiccarboxylic acid and polyol in which a part or all of at least onecomponent is an unsaturated polybasic carboxylic acid or unsaturatedpolyol.

Polybasic carboxylic acids include an unsaturated polybasic carboxylicacid and saturated polybasic carboxylic acid. Examples of the former aremaleic anhydride, fumaric acid, citraconic acid, itaconic acid, etc. Thelatter includes phthalic anhydride, isophthalic acid, terephthalic acid,adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid,etc. The detail of carboxylic acids are described in "Highpolymer DataHandbook, fundamental edition, p 259˜275 (Dicarboxylic acids)",published by Baihukan, Tokyo, Jan. 30, 1986.

Polyols include a saturated polyol and unsaturated polyol. The formerincludes ethylene glycol, propylene glycol and like alkanediol having 2to 8 carbon atoms. Examples of the latter are butenediol,3,4-dihydroxy-1,5-hexadiene, pentaerythritol diallyl ether, etc. Thedetail of polyols are shown in the above "Highpolymer Data Handbook,fundamental edition, p 283˜322 (Diols and polyols)".

Generally, the polyester is a condensation product of an unsaturatedpolybasic carboxylic acid or a mixture thereof with a saturatedpolybasic carboxylic acid, and a saturated polyol.

(ii) Polyester using an unsaturated monocarboxylic acid

The polyester is a condensation product of an unsaturated monocarboxylicacid, polybasic carboxylic acid and polyol.

The unsaturated monocarboxylic acids include acrylic acid, methacrylicacid, crotonic acid, cinnamic acid, half-ester of an unsaturateddicarboxylic acid such as monoalkyl (C₁˜8) ester of maleic acid,monoalkyl (C₁˜8) ester of fumaric acid, monoalkyl (C₁˜8) ester ofitaconic acid, etc.

As a polybasic carboxylic acid and polyol, same compounds are used asmentioned in (i).

Generally, the polyester is a condensation product of an unsaturatedmonocarboxylic acid, saturated polybasic carboxylic acid and saturatedpolyol.

(iii) Adduct of a polyepoxy compound and unsaturated monocarboxylic acid

Polyepoxy compounds include polyepoxy-hydrocarbon,polyepoxy-halogenohydrocarbon, polyepoxy-alcohol, polyepoxy-aldehyde,polyepoxy-carboxylic acid, etc. Polyepoxy compounds may be eithersaturated or unsaturated compounds and include a polymer, i.e., epoxyresin, as far as at least two epoxy groups are contained in themolecule. Examples of polyepoxy compounds are bisphenol A-diglycidylether, neopentyl glycol diglycidyl ether, vinylcyclohexene diepoxide,epoxidized soybean oil, etc. As unsaturated monocarboxylic acids, samecompounds are used as mentioned in (ii).

(iv) Polyetherpolyol unsaturated monocarboxylic acid ester

The ester is an ester of an adduct of polyol and alkylene oxide(polyetherpolyol), and unsaturated monocarboxylic acid.

Alkylene oxides include ethylene oxide, propylene oxide and likealkylene oxides having 2 to 8 carbon atoms, or those in which a part ofhydrogen atom is substituted with a halogen atom such as chlorine atom,etc.

As polyols and unsaturated monocarboxylic acids, same compounds are usedas mentioned in (i) and (ii).

(v) Unsaturated polyurethane

The unsaturated polyurethane is an adduct of a partial ester of a polyoland unsaturated monocarboxylic acid, and soluble or meltable compoundhaving a free isocyanate group (containing a linear or branchedstructure but no network structure). Examples of compounds having a freeisocyanate group are a polyisocyanate and adduct of polyisocyanate topolyol and/or polyetherpolyol.

Polyisocyanates include tolylenediisocyanate,dimethylenebenzenediisocyanate, diphenylmethanediisocyanate,hexahydrotolylenediisocyanate, dimethylenecyclohexanediisocyanate,dicyclohexylmethanediisocyanate, hexamethylenediisocyanate,isophoronediisocyanate, triphenylmethanetriisocyanate, compounds of theformulae ##STR20##

As polyols are used same compounds as mentioned in (i) and aspolyetherpolyols are employed same compounds as stated in (iv).

As partial esters of a polyol and unsaturated monocarboxylic acid arelisted 2-hydroxyethyl(meth)acrylate, trimethylolpropanedi(meth)acrylate, glycerine di(meth)acrylate, etc.

These compounds (i)˜(v) can be used singly or in mixture of at least twoof them.

In the present composition, the compound (3) is used preferably in anamount of about 1 to 99% (weight %, same as hereinafter), morepreferably about 20 to 60%.

In the curing of the above resin composition of the invention,ethylenically unsaturated compounds can be used, when required, as areactive diluent. The ethylenically unsaturated compounds includevarious known compounds and typical examples thereof are styrene,vinyltoluene, chlorostyrene, t-butylstyrene, α-methylstyrene,divinylbenzene, acrylic acid, methacrylic acid, methyl, ethyl,isopropyl, n-butyl, y-butyl, α-ethylhexyl, n-nonyl, n-decyl, lauryl orstearyl ester of acrylic acid or methacrylic acid, n-butoxyethyl,cyclohexyl, phenoxyethyl, tetrahydrofurfuryl, glycidyl, allyl, benzyl,tribromophenyl, 2,3-dichloropropyl, 3-chloro-2-hydroxypropyl ester ofacrylic acid or methacrylic acid, ethylene glycol mono(meth)acrylate,propylene glycol mono(meth)acrylate, diethylene glycolmono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethyleneglycol [Molecular weight (MW), 200˜1000] mono(meth)acrylate,polyethylene glycol (MW, 200˜1000) monomethyl ether mono(meth)acrylate,polypropylene glycol (MW, 200˜1000) mono(meth)acrylate, polypropyleneglycol (MW, 200˜1000) monomethyl ether mono(meth)acrylate, polyethyleneglycol (MW, 200˜1000) monoethyl ether mono(meth)acrylate, polypropyleneglycol (MW, 200˜1000) monoethyl ether mono(meth)acrylate, ethyleneglycol di(meth)acrylate, propylene glycol di(meth)acrylate,1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,polyethylene glycol di(meth)acrylate, polypropylene glycoldi(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate,trimethylolethane di(meth)acrylate, trimethylolethane tri(meth)acrylate,trimethylolpropane tri(meth)acrylate, diallyl phthalate, dibutylfumarate, vinyl acetate, etc. The reactive diluent is used preferably inan amount of about 1 to 95% by weight, more preferably about 5 to 80% byweight based on the total weight of the reactive diluent and theprepolymer.

In order to preserve the present composition in stable state, a knownpolymerization inhibitor can be added thereto. The amount thereof is0.001 to 2.5% by weight, preferably 0.005 to 1% by weight based on thetotal weight of the composition. Further, a coloring agent, dispersantand like conventional additives can be, as required, added to thepresent composition.

The present composition can be obtained by mixing the above ingredientsby a known method, for example, by use of a mixer, roll mill, ball mill,sand mill, high-speed impeller, etc.

The prepolymer of the present invention having at least one double bondin the molecule can be cured by a known method, for example, by heatingor with irradiation of ultraviolet rays, electron rays, X-rays,gamma-ray and like active energy rays.

In case of using the above electron rays, X-rays, gamma-ray or likeionized radioactive ray having high energy and releasing secondaryelectrons having absorbed in a substance, it is not necessary to use apolymerization initiator. However, in case the composition is cured byheating or with irradiation of ultraviolet rays, it is preferably to usea thermal polymerization initiator or photopolymerization initiator.

Examples of thermal polymerization initiators are methyl ethyl ketoneperoxide, cyclohexanone peroxide and like ketone peroxides, t-butylperbenzoate, t-butyl peroxy-2-ethylhexoate and like peresters, t-butylhydroperoxide, cumene hydroperoxide and like hydroperoxides, benzoylperoxide and like diacyl peroxides. The photopolymerization initiatorsinclude 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone andlike benzoin alkyl ethers, diethoxyacetophenone and like acetophenones,benzophenone and like ketones, 2-chlorothioxanthone and likethioxanthones, etc. The initiator is used preferably in an amount ofabout 0.001 to 20% by weight, more preferably about 0.1 to 10% by weightbased on the total amount of the prepolymer and reactive diluent.

The curing is conducted usually at a temperature from room temperatureto 250° C., preferably from room temperature to 180° C., despite thatany of heat, light or active energy rays is used.

The compound (1) is useful as a starting material for a prepolymer andcured product. For example, a homoprepolymer or coprepolymer of thecompound (1) is employed for the preparation of a fiber reinforcedplastic, glass cloth prepreg, etc.

The prepolymer contains a side chain which has a carbon-carbon doublebond in the terminal, exhibits cross-linking ability and affords a curedproduct. Further, the prepolymer has a perfluoroalkenyloxy chain as theother side chain which gives an excellent water-resistance to the curedproduct. The cured product obtained from the present prepolymer haswater-resistance which is much superior to that of a cured productprepared from the conventional diallyl phthalate. Even the prepolymercontaining about 50% by weight of the repeating unit (6) provides acuring product which is about 1/10 in water absorbency than theconventional product.

The invention will be described below with reference to Examples andComparison Examples in which parts are all by weight, unless otherwisespecified.

EXAMPLE 1

Into a reaction vessel equipped with a stirrer, condenser andthermometer was placed 0.2 mole of 5-hydroxy-isophthalic acid. Theretowere added 0.6 mole of allyl alcohol, 300 ml of toluene, 1.3 g ofsulfuric acid and 0.2 g of p-methoxyphenol and the mixture was refluxedwith heating. A mixture of toluene and water was distilled off andcooled with a condenser, and toluene was separated from water andreturned contineously to the reaction vessel. The mixture was heated for8 hours. and then allowed to cool. At this point, total of distilledwater was 7 ml. After the reaction mixture was washed with a saturatedaqueous solution of sodium chloride until the aqueous layer did notindicate acidic, toluene was distilled at a reduced pressure. Theresulting concentrate was distilled at a reduced pressure to obtain 27 g(yield 52%) of diallyl 5-hydroxy-isophthalate. b.p. 202°˜205° C./5 mmHg.

¹ H-NMR (TMS standard, in acetone-d₆, δ ppm) ##STR21##

The obtained diallyl 5-hydroxy-isophthalate (26 g) was dissolved into 90ml of dimethlformamide and thereto was added 31 g of triethylamine. Tothe mixture was added dropwise 45 g of hexafluoropropene trimer withstirring at room temperature in a period of 10 minutes. The mixture wasfurther stirred for 2 hours and then poured into a large amount of adiluted aqueous solution of hydrochloric acid to obtain oilyprecipitates. The precipitates were separated, washed with water anddistilled at a reduced pressure to give 41 g (yield 59%) of diallyl5-(perfluorononenyloxy)isophthalate (Compound A). b.p. 150°˜152° C./4mmHg.

¹⁹ F-NMR (external standard CF₃ COOH, in CDCl₃) Chemical shift (δ ppm)is shown in which high magnetic field is indicated by a plus value.##STR22##

EXAMPLE 2

The reaction was conducted in the same manner as in Example 1 exceptthat 4-hydroxy-phthalic acid was used in place of 5-hydroxy-isophthalicacid to obtain diallyl 4-(perfluorononenyloxy)phthalate (Compound B).b.p. 160°˜162° C./7 mmHg. ##STR23##

EXAMPLE 3

The reaction was conducted in the same manner as in Example 1 exceptthat 30 g of hexafluoropropene dimer was used in place of the trimerthereof and the reaction with diallyl 5-hydroxy-isophthalate wasconducted at 0° to 4° C. to obtain 39 g of diallyl5-(perfluorohexenyloxy)isophthalate (Compound C). b.p. 128°˜ 131° C./5mmHg.

¹⁹ F-NMR (external standard CF₃ COOH, in CDCl₃, δ ppm) ##STR24##

EXAMPLE 4

The reaction was conducted in the same manner as in Example 2 exceptthat 50 g of tetrafluoroethylene pentamer was used in place ofhexafluoropropene trimer to obtain diallyl4-(perfluorodecenyloxy)phthalate (Compound D). b. p. 165°˜167° C./6mmHg.

EXAMPLE 5

Into a vessel equipped with a stirrer and condenser were placed CompoundA (250 g), diallyl terephthalate (250 g), benzoyl peroxide (7 g),dibutyltin dilaurate (6 g) and water (250 g), and the mixture wasreacted at 85° C. for 5 hours. After completion of the reaction, themixture was cooled to room temperature and acetone (50 g) was addedthereto. The organic layer was added dropwise to a large amount ofmethanol with stirring. The resulting precipitates were filtered, washedwith methanol, dried at a reduced pressure and pulverized to obtain 120g of white powder. The powder was 66 in iodine value, 8.6×10³ in numberaverage molecular weight (Mn), 5.3×10⁴ in weight average molecularweight (Mw) in term of polystyrene with use of gel permeationchromatography and 18.5 wt % in fluorine content. Accordingly, the abovewhite powder was a prepolymer in which Compound A and diallylterephthalate were contained in molar ratio of 1:4.3. To a solution ofthe prepolymer (50 parts) and diallyl terephthalate (50 parts) was addedbenzoyl peroxide (2 parts). The mixture was poured into a Petri dishhaving internal diameter of 50 mm and heated at 90° C. for 8 hours toobtain a casting plate which was 50 mm in diameter and 3 mm inthickness.

EXAMPLE 6

White powder (102 g) was obtained in the same manner as in Example 5except that Compound B (250 g) was used as diallyl aromaticfluorine-containing dicarboxylate and the reaction was conducted for 4hours. The powder was 70 in iodine value, 7.3×10³ in Mn, 4.4×10⁴ in Mwand 18.6 wt % in fluorine content. Accordingly, the above white powderwas a prepolymer in which Compound B and diallyl terephthalate werecontained in molar ratio of 1:4.3. A casting plate was obtained in thesame manner as in Example 5 with use of the prepolymer.

EXAMPLE 7

White powder (148 g) was obtained in the same manner as in Example 6except that Compound B (375 g) and diallyl terephthalate (125 g) wereused. The powder was 49 in iodine value, 1.1×10⁴ in Mn, 4.6×10⁵ in Mwand 31.4 wt % in fluorine content. Accordingly, the above white powderwas a prepolymer in which Compound B and diallyl terephthalate werecontained in molar ratio of 1:1.4. A casting plate was obtained in thesame manner as in Example 5 with use of the prepolymer.

EXAMPLE 8

White powder (118 g) was obtained in the same manner as in Example 5except that diallyl phthalate (125 g) and diallyl isophthalate (125 g)were used in place of diallyl terephthalate. The powder was 65 in iodinevalue, 7.2×10³ in Mn, 4.2×10⁴ in Mw and 18.7 wt % in fluorine content.Accordingly, the above white powder was a prepolymer in which Compound Aand diallyl esters were contained in molar ratio of 1:4.3. A castingplate was obtained in the same manner as in Example 5 with use of theprepolymer.

EXAMPLE 9

White powder (121 g) was obtained in the same manner as in Example 5except that diallyl isophthalate was used in place of diallylterephthalate. The powder was 72 in iodine value, 5.6×10³ in Mn, 6.1×10⁴in Mw and 18.5 wt % in fluorine content. Accordingly, the above whitepowder was a prepolymer in which Compound A and diallyl isophthalatewere contained in molar ratio of 1:4.3. A casting plate was obtained inthe same manner as in Example 5 with use of the prepolymer.

EXAMPLE 10

A prepolymer (87 g) of Compound B only was prepared in the same manneras in Example 6 except that Compound B was used as a sole component ofaromatic dicarboxylate without use of diallyl terephthalate. The powderwas 28 in iodine value, 2.4×10³ in Mn, 4.8×10³ in Mw and 45.9 wt % influorine content. The prepolymer (50 parts) and Compound B (50 parts)were mixed homogeneously with heating and benzoyl peroxide (2 parts) wasadded thereto. The mixture was heated at 90° C. for 8 hours to obtain acasting plate.

EXAMPLE 11

White powder (108 g) was obtained in the same manner as in Example 5with use of Compound C (300 g), diallyl terephathalate (200 g), benzoylperoxide (7 g), dibutyltin dilaurate (6 g) and water (250 g). The powderwas 71 in iodine value, 9.2×10³ in Mn , 5.9×10⁴ in Mw and 19.8 wt % influorine content. Accordingly, the above white powder was a prepolymerin which Compound C and diallyl terephthalate were contained in molarratio of 1:2.1. The prepolymer (60 parts) and diallyl terephthalate (40parts) were mixed and benzoyl peroxide (2 parts) was added thereto. Acasting plate was prepared in the same manner as in Example 5 with useof the mixture.

EXAMPLE 12 ##STR25##

In Compound D, perfluoroalkenyloxy group X is derived from pentamer oftetrafluoroethylene. A prepolymer (107 g) of Compound D only wasprepared in the same manner as in Example 10 except that Compound D (500g) was used and the reaction was conducted for 6 hours. The powder was26 in iodine value, 3.2×10³ in Mn, 6.7×10³ in Mw and 48.5 wt % influorine content. The prepolymer (70 parts) and Compound D (30 parts)were mixed homogeneously with heating and benzoyl peroxide (2 parts) wasadded thereto. A casting plate was prepared in the same manner as inExample 5 with use of the mixture.

COMPARISON EXAMPLE 1

Into diallyl terephthalate (50 parts) was dissolved 50 parts of diallylphthalate prepolymer [trade name, DAISO DAP A, Osaka Soda Co., Ltd.,Mn=6.7×10³, Mw=2.6×10⁴, iodine value 61] and benzoyl peroxide (2 parts)was added thereto. A casting plate was prepared in the same manner as inExample 5 with use of the mixture.

COMPARISON EXAMPLE 2

A casting plate was prepared in the same manner as in Comparison Example1 except that diallyl terephthalate polymer [trade name, DAPREN, OsakaSoda Co., Ltd., Mn=7.3×10³, Mw=2.5×10⁵, iodine value 51] was used inplace of DAISO DAP A.

Casting plates prepared in Examples 5 to 12 and Comparison Examples 1and 2 were checked for water absorbency at 23° C. according to JISK-6911. The results were given in Table 1.

                  TABLE 1                                                         ______________________________________                                        Water                      Water                                              absorbency                 absorbency                                         (wt %)                     (wt %)                                             ______________________________________                                        Ex. 5  0.03          Ex. 10    <0.01                                          Ex. 6  0.03          Ex. 11    0.04                                           Ex. 7  0.01          Ex. 12    <0.01                                          Ex. 8  0.04          Com. Ex. 1                                                                              0.33                                           Ex. 9  0.03          Com. Ex. 2                                                                              0.41                                           ______________________________________                                    

EXAMPLE 13

A ultraviolet-ray curable resin composition (I) was prepared accordingto the following formulation.

    ______________________________________                                        *   Oligoester acrylate [trade name, ARONIX                                                                 50                                                  M-6420 X, viscosity 4 × 10.sup.4 cps/50° C.,                     Toagosei Chemical Industry Co., Ltd.]                                     *   Compound (A)              35                                              *   Trimethylolpropane triacrylate                                                                          5                                               *   2-Hydroxyethyl acrylate   3                                               *   Methyl o-benzoylbenzoate  5                                               *   Diethylaminoethyl methacrylate                                                                          2                                                                             100    parts                                    ______________________________________                                    

Composition (I) was applied by a bar coater to a glass plate in athickness of 20 μm and the coating film was cured sufficiently bysubjecting the film to pass under a high-voltage mercury lamp (80 W/cm)three times, the film being placed on a conveyor moving at 5 m/min.

EXAMPLE 14

A ultraviolet-ray curable resin composition (II) was prepared accordingto the following formulation.

    ______________________________________                                        *   Unsaturated epoxy resin [trade name Diclite                                                             50                                                  UE-8200, Dainippon Ink & Chemicals Inc.]                                  *   Compound (B)              30                                              *   1,6-Hexanediol diacrylate 10                                              *   2-Hydroxyethylacryloyl phosphate                                                                        3                                               *   Methyl o-benzoylbenzoate  5                                               *   Triethanolamine           2                                                                             100    parts                                    ______________________________________                                    

Composition (II) was applied by a bar coater to a degreased soft steelplate in a thickness of 20 μm and the coating film was cured in the samemanner as in Example 13.

EXAMPLE 15

A thermosetting resin composition (III) was prepared according to thefollowing formulation.

    ______________________________________                                        *     Maleic acid-propylene glycol type un-                                                                40                                                     saturated polyester resin                                                     (acid value 18.5 mg KOH/g)                                              *     Compound (C)           35                                               *     Styrene                20                                               *     Methyl ethyl ketone peroxide                                                                         3                                                *     Dimethylaniline (0.5% solution)                                                                      1                                                *     Cobalt naphthenate (Co content 5%)                                                                   1                                                                             100    parts                                     ______________________________________                                    

Composition (III) was applied by a bar coater to a degreased soft steelplate in a thickness of 100 μm and the coating film was allowed to standin a desiccator at 30° C. for 10 hours, the air in the desiccator beingreplaced by nitrogen preveously.

EXAMPLE 16

    ______________________________________                                        *   Urethane acrylate [trade name, ARONIX                                                                  45                                                   M-1100, viscosity 8˜12 × 10.sup.4 cps/50° C.,              Toagosei Chemical Industry Co., Ltd.]                                     *   Compound (A)             25                                               *   Trimethylolpropane triacrylate                                                                         20                                               *   2-Hydroxyethylacryloyl phosphate                                                                       3                                                *   Methyl o-benzoylbenzoate 5                                                *   Triethanolamine          2                                                                             100     parts                                    ______________________________________                                    

A ultraviolet-ray curable resin composition (IV) was prepared accordingto the above formulation and a coating film was cured in the same manneras in Example 13.

EXAMPLE 17

    ______________________________________                                        *   Polyether acrylate [trade name, ARONIX                                                                 30                                                   M-220, viscosity 10˜20 cps/25° C.,                               Toagosei Chemical Industry Co., Ltd.]                                     *   Compound (B)             50                                               *   Trimethylolpropane triacrylate                                                                         13                                               *   Methyl o-benzoylbenzoate 5                                                *   Diethylaminoethyl methacrylate                                                                         2                                                                             100     parts                                    ______________________________________                                    

A ultraviolet-ray curable resin composition (V) was prepared accordingto the above formulation and the composition (V) was applied by a barcoater to a glass plate in a thickness of 20 μm, and the coating filmwas cured in the same manner as in Example 13.

COMPARISON EXAMPLE 3

The procedure was conducted in the same manner as in Example 13 exceptthat diallyl isophthalate was used in place of Compound (A).

COMPARISON EXAMPLE 4

The procedure was conducted in the same manner as in Example 14 exceptthat diallyl phthalate was used in place of Compound (B).

COMPARISON EXAMPLE 5

The procedure was conducted in the same manner as in Example 15 exceptthat diallyl isophthalate was used in place of Compound (C).

COMPARISON EXAMPLE 6

The procedure was conducted in the same manner as in Example 16 exceptthat diallyl isophthalate was used in place of Compound (A).

COMPARISON EXAMPLE 7

The procedure was conducted in the same manner as in Example 17 exceptthat diallyl isophthalate was used in place of Compound (B).

EXAMPLE 18

A ultraviolet-ray curable resin composition (VI) was prepared accordingto the following formulation and a coating film was cured in the samemanner as in Example 13.

    ______________________________________                                        *     Polyethylene glycol diacrylate                                                                       40                                                     (average molecular weight: 510)                                         *     Compound (A)           20                                               *     Trimethylolpropane triacrylate                                                                       30                                               *     Methyl o-benzoylbenzoate                                                                             6                                                *     Diethylaminoethyl methacrylate                                                                       4                                                                             100    parts                                     ______________________________________                                    

EXAMPLE 19

A mixture of one mole of maleic anhydride, one mole of phthalicanhydride and 2.16 moles of diethylene glycol was heated to 150° C. in aperiod of one hour under nitrogen atmosphere and then was maintained atthe same temperature for 2 hours. Then the mixture was heated at 190° C.for 3 hours. As a residue was obtained an unsaturated polyester havingan acid value of 55.7 mg KOH/g and hydroxyl value of 84.9 mg KOH/g. Athermosetting resin composition (VII) and a cured product thereof wereobtained in the same manner as in Example 15 except that the aboveunsaturated polyester was used in place of the polyester of Example 15.

EXAMPLE 20

A ultraviolet-ray curable resin composition (VIII) was preparedaccording to the following formulation and a coating film was cured inthe same manner as in Example 13.

    ______________________________________                                        *Urethane acrylate      40                                                     ##STR26##                                                                     ##STR27##                                                                     ##STR28##                                                                    (n is 1, 2 and 3, average thereof is 2)                                       *Compound (A)           20                                                    *Trimethylolpropane triacrylate                                                                       15                                                    *Tetrahydrofurfuryl acrylate                                                                          20                                                    *Benzyl dimethyl ketal  5                                                                             100    parts                                          ______________________________________                                    

EXAMPLE 21

A ultraviolet-ray curable resin composition (IX) was prepared in thesame manner as in Example 13 except that 50 parts of the oligoesteracrylate having the formula below [trade name, Viscoat #3700, OsakaOrganic Chemical Ind. Co., Ltd.] was used in place of the oligoesteracrylate of Example 13. A coating film was cured in the same manner asin Example 13. ##STR29##

EXAMPLE 22

A ultraviolet-ray curable resin composition (X) was prepared accordingto the following formulation and a coating film was cured in the samemanner as in Example 14.

    ______________________________________                                        *Epoxy acrylate [trade name, Viscoat #540, Osaka                                                         40                                                 Organic Chemical Ind. Co., Ltd.]                                              CH.sub.2CHCOOCH.sub.2 CH(OH)CH.sub.2                                           ##STR30##                                                                    (viscosity: 2 × 10.sup.4 cps/50° C.)                             *Compound (B)              30                                                 *1,6-Hexanediol diacrylate 20                                                 *2-Hydroxyethylacryloyl phosphate                                                                        3                                                  *Methyl o-benzoylbenzoate  5                                                  *Triethanolamine           2                                                                             100    parts                                       ______________________________________                                    

ADHESION AND WATER-RESISTANCE TESTS

Curable resin compositions were checked for adhesiveness to a substratebefore boiling in water according to the following cross-cut peelingtest and were checked for water-resistance by observing an appearance ofa coating after boiling in water. The results were given in Table 2. Thepresent invention showed excellent effects in which the water-resistancewas improved by using the compound (3).

Adhesion:

Adhesiveness was checked by cross-cut peeling test. The coating wascross-cut to the surface of the substrate in 100 pieces each 1×1 mm. Acellophane tape was adhered to the cross-cut portion and then peeled offquickly and the remained pieces were counted. Number of the remainedpieces was shown.

Water-resistance:

Appearance of the coating after immersed in boiling water was shown.

◯ No change

Δ Coating was partially whited and swollen

X Coating was peeled off from the substrate

                  TABLE 2                                                         ______________________________________                                                    Adhesiveness                                                                  (number of Water-                                                             remained pieces)                                                                         resistance                                             ______________________________________                                        Ex.       13      100          ◯                                            14      100          ◯                                            15      100          ◯                                            16      100          ◯                                            17      100          ◯                                            18      100          ◯                                            19      100          ◯                                            20      100          ◯                                            21      100          ◯                                            22      100          ◯                                  Com. Ex.   3      100          Δ                                                   4      100          Δ                                                   5      100          Δ                                                   6      100          Δ                                                   7      100          X                                              ______________________________________                                    

We claim:
 1. A curable resin composition which comprises a prepolymerhaving at least one carbon-carbon-double bond in the molecule anddiallyl aromatic fluorine-containing dicarboxylate represented by theformula (3): ##STR31## where X is a perfluoroalkenyl group having 6-14carbon atoms.
 2. A composition as defined in claim 1 wherein theprepolymer is a polyester of unsaturated polybasic carboxylic acid,polyester of unsaturated polyol, polyester of unsaturated monocarboxylicacid, adduct of a polyepoxy compound and an unsaturated monocarboxylicacid, polyester of polyether polyol and an unsaturated monocarboxylicacid or unsaturated polyurethane.
 3. A composition as defined in claim 1which further comprises a reactive diluent.